JP3920874B2 - Heavy metal immobilization treatment agent, method for producing the same heavy metal immobilization treatment agent, and heavy metal immobilization treatment method - Google Patents
Heavy metal immobilization treatment agent, method for producing the same heavy metal immobilization treatment agent, and heavy metal immobilization treatment method Download PDFInfo
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- JP3920874B2 JP3920874B2 JP2004157749A JP2004157749A JP3920874B2 JP 3920874 B2 JP3920874 B2 JP 3920874B2 JP 2004157749 A JP2004157749 A JP 2004157749A JP 2004157749 A JP2004157749 A JP 2004157749A JP 3920874 B2 JP3920874 B2 JP 3920874B2
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- 229910001385 heavy metal Inorganic materials 0.000 title claims description 63
- 238000000034 method Methods 0.000 title claims description 16
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 75
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 74
- 239000011593 sulfur Substances 0.000 claims description 74
- 229910052717 sulfur Inorganic materials 0.000 claims description 74
- 239000011575 calcium Substances 0.000 claims description 37
- 239000002994 raw material Substances 0.000 claims description 33
- 239000005077 polysulfide Substances 0.000 claims description 30
- 229920001021 polysulfide Polymers 0.000 claims description 30
- 150000008117 polysulfides Polymers 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 239000003513 alkali Substances 0.000 claims description 27
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 26
- 229910052791 calcium Inorganic materials 0.000 claims description 26
- 229910001868 water Inorganic materials 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 22
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 20
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 20
- 239000011777 magnesium Substances 0.000 claims description 20
- 229910052749 magnesium Inorganic materials 0.000 claims description 20
- 239000011734 sodium Substances 0.000 claims description 20
- 229910052708 sodium Inorganic materials 0.000 claims description 20
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 19
- 239000011591 potassium Substances 0.000 claims description 19
- 229910052700 potassium Inorganic materials 0.000 claims description 19
- 230000003100 immobilizing effect Effects 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 10
- 239000002699 waste material Substances 0.000 claims description 9
- 238000010828 elution Methods 0.000 claims description 7
- 239000004927 clay Substances 0.000 claims description 5
- 239000004575 stone Substances 0.000 claims description 4
- 239000004576 sand Substances 0.000 claims description 3
- 239000002956 ash Substances 0.000 description 54
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 26
- 239000000920 calcium hydroxide Substances 0.000 description 26
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 26
- 235000011116 calcium hydroxide Nutrition 0.000 description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 18
- 239000000126 substance Substances 0.000 description 13
- 239000007788 liquid Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 239000010881 fly ash Substances 0.000 description 8
- 239000002244 precipitate Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 7
- 239000000347 magnesium hydroxide Substances 0.000 description 7
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 7
- 230000007423 decrease Effects 0.000 description 6
- 230000002378 acidificating effect Effects 0.000 description 5
- 239000002440 industrial waste Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000003245 coal Substances 0.000 description 4
- 239000000428 dust Substances 0.000 description 4
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 239000010802 sludge Substances 0.000 description 4
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- -1 embankments Substances 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000012744 reinforcing agent Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000011449 brick Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000002738 chelating agent Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 229910052976 metal sulfide Inorganic materials 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000011435 rock Substances 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000010344 co-firing Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- HRKQOINLCJTGBK-UHFFFAOYSA-N dihydroxidosulfur Chemical class OSO HRKQOINLCJTGBK-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000007922 dissolution test Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000000077 insect repellent Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 229940016373 potassium polysulfide Drugs 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Landscapes
- Processing Of Solid Wastes (AREA)
- Soil Conditioners And Soil-Stabilizing Materials (AREA)
Description
本発明は、多硫化物（但し、Sx（ｘ＝２〜１２））を主成分とする処理剤及びその製造方法に関するものである。 The present invention relates to a treatment agent containing polysulfide (provided that Sx (x = 2 to 12)) as a main component and a method for producing the same.
現状において、硫黄を利用した重金属安定剤は、通称“キレート剤”として有機系，無機系，その反応性向上目的では、高多硫化や応用技術開発に見られるように種々の技術的開発及検討がなされているのが現状であるが、いずれもその反応安定性及コストダウン、を目的としている（たとえば、特許文献１参照。）。 At present, heavy metal stabilizers using sulfur are known as “chelating agents”, organic and inorganic, and for the purpose of improving their reactivity, various technical developments and examinations as seen in high polysulfurization and applied technology development However, all are aimed at the stability of the reaction and cost reduction (see, for example, Patent Document 1).
一方、これらの開発技術は薬液の使用条件等を、安定的で優位なものとすることを目的として、硫黄をベースとした母液（例えばカルシウムや、マグネシウム、ナトリウム反応体）と鉄及びその酸化反応体や硫化反応体を組合せて使用することで、目的を達しようという手法であり、強アルカリ灰や強酸性灰の処理において、処理コストの増大をやむなしとした解決法といえる。 On the other hand, these developed technologies aim to make the use conditions of chemical solutions stable and superior, and sulfur-based mother liquors (for example, calcium, magnesium, sodium reactants), iron and their oxidation reactions This is a technique to achieve the purpose by using a combination of a solid body and a sulfurized reactant, and can be said to be a solution that unavoidably increases the processing cost in the treatment of strong alkali ash and strong acid ash.
特に、焼却炉や、発電所等から発生する、強アルカリ灰の処理に関しては、重金属の電気的溶出特性から見て、単独の薬剤による処理は難しく事前又は事後のＰＨ調整が必要とされてきた。 In particular, regarding the treatment of strong alkaline ash generated from incinerators, power plants, etc., it has been difficult to treat with a single agent in view of the electrical elution characteristics of heavy metals, and it has been necessary to adjust the pH in advance or afterwards. .
また、従来より、多硫化物を主成分とする処理剤は、様々な用途で広く使用されてきているが、これらの処理剤に含有される多硫化物は、全てSx（ｘ＝２〜５）を含有するものであった。 Conventionally, treatment agents mainly composed of polysulfides have been widely used in various applications, but all of the polysulfides contained in these treatment agents are Sx (x = 2 to 5). ).
たとえば、汚泥、粉塵、集塵などの廃棄物は、その廃棄物中に含有される鉛・亜鉛・水銀・クロム・マンガン・コバルト・ニッケルなどの重金属が溶出することがないように、セメント固化法、薬剤添加法、溶融固化法、溶媒抽出法などの処理方法を用いて中間処理された後に埋め立て処分されていた（たとえば、特許文献２参照）が、この薬剤添加法においては、消石灰と硫黄とを混合することによって生成したCaSx（ｘ＝２〜５）を主成分とする廃棄物処理剤が使用されていた（たとえば、特許文献３参照)。
ここで問題となるのは、脱硫や脱塩目的で混合された、消石灰を初めとするカルシウム成分であり、硫黄系キレート剤は、その反応性の良さが原因となり、目的とする重金属類と反応する前に、カルシウムと反応することとなり、薬液の使用量が、これらカルシウム体を含まない場合に比較し3倍〜10倍に拡大することであった。 The problem here is calcium components, such as slaked lime, mixed for the purpose of desulfurization and desalination, and sulfur-based chelating agents react with the intended heavy metals due to their good reactivity. It would react with calcium before doing so, and the amount of drug solution used would be 3 to 10 times larger than when these calcium bodies were not included.
また、処理剤に含有される多硫化物がSx（ｘ＝２〜５）を含有するものであったのは、Sx（ｘ＝２〜５）を含有する多硫化物、現実的には、Sx（ｘ＝２〜３）を含有する多硫化物しか安定的かつ安全に生成することができなかったことによるものである。 In addition, the polysulfide contained in the treatment agent contains Sx (x = 2 to 5) because the polysulfide containing Sx (x = 2 to 5) This is because only polysulfides containing Sx (x = 2 to 3) could be produced stably and safely.
すなわち、上記従来の消石灰と硫黄とを混合することによって生成したCaSx（ｘ＝２〜５）を主成分とする処理剤にあっては、消石灰と硫黄とを熱水中で混合するだけで比較的容易に生成することができる反面、その生成過程で硫化水素をはじめとする硫黄の水酸化物を含有する蒸気が発生していた。 That is, in the treatment agent mainly composed of CaSx (x = 2 to 5) generated by mixing the above-described conventional slaked lime and sulfur, a comparison is made by simply mixing slaked lime and sulfur in hot water. Although it can be produced easily, steam containing sulfur hydroxide such as hydrogen sulfide was generated during the production process.
そのため、水酸化物の蒸発によって当然に水酸基が不足を生じ、それを補うために水酸化物を補充することによって硫黄の結合数の低いSx（ｘ＝２〜５）を含有する多硫化物が安定して生成されてしまっていた。 For this reason, the hydroxyl group is naturally deficient due to the evaporation of the hydroxide, and the polysulfide containing Sx (x = 2 to 5) having a low number of sulfur bonds is obtained by replenishing the hydroxide to make up for it. It was generated stably.
また、従来においては、処理剤の生成過程で硫黄の水酸化物や水素反応物を含有する蒸気の処理が必要となり、そのための設備投資や処理労力や処理時間を要することになり、さらには、蒸気の蒸発によって水溶液の体積が減少することになり、水と硫黄と水酸化物との必要バランスを保持できなくなり、結果的に処理剤の製造効率が低減していた。 In addition, conventionally, it is necessary to process steam containing sulfur hydroxide or hydrogen reactant in the process of generating the treatment agent, which requires capital investment, processing labor and processing time, The volume of the aqueous solution is reduced by evaporation of the vapor, and the necessary balance of water, sulfur, and hydroxide cannot be maintained, and as a result, the manufacturing efficiency of the treatment agent is reduced.
そして、多硫化物を主成分とする処理剤では、硫黄の結合数（ｘの値）の低下によって被処理物の処理に要する処理剤の量が増大してしまい、処理コストの増大を招いていた。 And in the processing agent which has a polysulfide as a main component, the quantity of the processing agent required for processing of a to-be-processed object will increase by the fall of the number of sulfur bonds (value of x), and has caused the increase in processing cost. It was.
また、従来においては、水酸化カルシウムを例にとると、温度の上昇に伴って硫黄の溶解度は上昇するのに対して消石灰の溶解度は低下するといった硫黄と消石灰の溶解特性を考慮することなくただ単に硫黄と消石灰とを混合させていたため、全ての消石灰が硫黄と反応せずに、硫黄粒子の表面に消石灰がコーティングされた状態で固体化してしまうものが生じ、硫黄と消石灰との反応が良好に行われず、Sx（ｘ＝２〜５）を含有する多硫化物が安定して生成されなかった。特に、硫黄と消石灰との反応を促進するためにはｐＨを確認しながら消石灰を数回に分けて徐々に投入する必要があり、このために反応槽の蓋を開閉することになり、有害な硫化水素を含む蒸気の発生による危険を伴い、また、反応温度の低下による製造時間の増大を招いていた。 Conventionally, when calcium hydroxide is taken as an example, the solubility of sulfur increases with increasing temperature, while the solubility of slaked lime decreases, while the solubility of sulfur and slaked lime decreases. Since only sulfur and slaked lime were mixed, all slaked lime does not react with sulfur, and some slaked lime is coated on the surface of the sulfur particles, resulting in a good reaction between sulfur and slaked lime. The polysulfide containing Sx (x = 2 to 5) was not stably produced. In particular, in order to promote the reaction between sulfur and slaked lime, it is necessary to gradually add slaked lime several times while confirming the pH, which opens and closes the lid of the reaction tank, which is harmful. There is a danger due to the generation of steam containing hydrogen sulfide, and the production time is increased due to a decrease in the reaction temperature.
さらに、従来においては、硫黄と消石灰との反応速度が硫黄の溶解度の上昇に伴って低下することから、反応速度の低下とともに不足した水酸基を供給するために必要以上の消石灰を溶解させることとなり、その分硫黄の溶解度が理論的溶解限度よりも低くなってしまう。これらの理由によってSx（ｘ＝２〜５）を含有する多硫化物のｘの値が低下し、それに伴って被処理物の処理に要する処理剤の量が増大してしまい、高濃度の多硫化物を生成するために必要な反応時間が理論的な反応時間の約９〜１２倍（９０分〜１２０分）も要するようになり、処理コストの増大を招いていた。 Furthermore, in the past, the reaction rate of sulfur and slaked lime decreases with an increase in the solubility of sulfur, so that more slaked lime is dissolved than necessary to supply the deficient hydroxyl group with a decrease in the reaction rate, As a result, the solubility of sulfur becomes lower than the theoretical solubility limit. For these reasons, the value of x of polysulfides containing Sx (x = 2 to 5) decreases, and accordingly, the amount of processing agent required for processing the object to be processed increases, resulting in a high concentration of many. The reaction time required for producing sulfides is about 9 to 12 times (90 minutes to 120 minutes) of the theoretical reaction time, leading to an increase in processing costs.
しかも、従来においては、処理剤の使用量の増大に伴って被処理物のｐＨがアルカリ側へ変化してしまい、重金属の再溶出を招くおそれがあり、そのために、ｐＨ調整剤の使用やセメント剤の使用を余儀なくされ、体積の増大を招くことで埋め立て処理を行う上で不利益となっていた。 In addition, conventionally, the pH of the object to be treated may change to the alkali side with an increase in the amount of treatment agent used, which may lead to re-elution of heavy metals. The use of the agent was unavoidable, and the volume was increased, which was disadvantageous for the landfill process.
また、請求項１に係る本発明では、アルカリ灰を原料として熱水中又は水蒸気中で硫黄と反応させて生成した多硫化物（但し、Sx（ｘ＝２〜１２））を主成分とし、重金属を含有する被処理物に混合することによって重金属を固定化して被処理物からの溶出を防止することを特徴とする重金属固定化処理剤を提供するものである。 In the present invention according to claim 1 , the main component is polysulfide (where Sx (x = 2 to 12)) produced by reacting with alkali ash as a raw material and sulfur in hot water or steam. The present invention provides a heavy metal immobilization treatment agent characterized by immobilizing heavy metal by mixing with an object to be treated containing heavy metal to prevent elution from the object to be treated.
また、請求項２に係る本発明では、反応装置内で原料となるアルカリ灰と硫黄とを混合し、原料となるアルカリ灰中のカルシウム、カリウム、ナトリウム、又はマグネシウムと硫黄を熱水中又は水蒸気中で反応させて生成した重金属と反応して固定化する重金属固定化処理剤を提供するものである。 Moreover, in this invention which concerns on Claim 2 , the alkaline ash and sulfur which are raw materials in a reaction apparatus are mixed, and calcium, potassium, sodium, or magnesium and sulfur in the alkaline ash used as a raw material are made into hot water or water vapor | steam. The present invention provides a heavy metal immobilization treatment agent that reacts and immobilizes with a heavy metal produced by reaction in the medium.
また、請求項３に係る本発明では、反応装置内で原料となるアルカリ灰と硫黄とを混合し、原料となるアルカリ灰中のカルシウム、カリウム、ナトリウム、又はマグネシウムと硫黄を熱水中又は水蒸気中で反応させて生成する重金属と反応して固定化する重金属固定化処理剤の製造方法を提供するものである。 Moreover, in this invention which concerns on Claim 3 , the alkali ash and sulfur which are raw materials in a reaction apparatus are mixed, and calcium, potassium, sodium, or magnesium and sulfur in the alkali ash used as a raw material are made into hot water or water vapor | steam. The present invention provides a method for producing a heavy metal immobilization treatment agent that reacts and immobilizes with a heavy metal produced by reaction in the medium.
また、請求項４に係る本発明では、反応装置内で原料となるアルカリ灰と硫黄とを混合し、原料となるアルカリ灰中のカルシウム、カリウム、ナトリウム、又はマグネシウムと硫黄を熱水中又は水蒸気中で反応させて重金属固定化処理剤を生成し、この重金属固定化処理剤を用いて原料とは異なるアルカリ灰中の重金属を固定化する重金属固定化処理方法を提供するものである。 Moreover, in this invention which concerns on Claim 4 , the alkaline ash and sulfur which are raw materials in a reaction apparatus are mixed, and calcium, potassium, sodium, or magnesium and sulfur in the alkaline ash used as raw materials are made into hot water or water vapor | steam. The present invention provides a heavy metal immobilization treatment method in which a heavy metal immobilization treatment agent is produced by reacting in a heavy metal, and a heavy metal in alkali ash different from the raw material is immobilized using the heavy metal immobilization treatment agent.
また、請求項５に係る本発明では、前記反応中又は反応後に、石、粘土、真砂、又は灰を混入することを特徴とする請求項４に記載の重金属固定化処理方法を提供するものである。 The present invention according to claim 5 provides the heavy metal immobilization treatment method according to claim 4 , wherein stone, clay, sand, or ash is mixed during or after the reaction. is there.
また、請求項６に係る本発明では、反応装置内で廃棄物としてのアルカリ灰の一部と硫黄とを混合し、このアルカリ灰中のカルシウム、カリウム、ナトリウム、又はマグネシウムと硫黄を熱水中又は水蒸気中で反応させて重金属固定化処理剤を生成し、この重金属固定化処理剤を用いて残りのアルカリ灰中の重金属を固定化する重金属固定化処理方法を提供するものである。 Further, in the present invention according to claim 6 , a part of alkaline ash as waste and sulfur are mixed in the reactor, and calcium, potassium, sodium, or magnesium and sulfur in the alkaline ash are mixed with hot water. Alternatively, the present invention provides a heavy metal immobilization treatment method in which a heavy metal immobilization treatment agent is produced by reacting in water vapor, and the heavy metal immobilization treatment agent is immobilized using the heavy metal immobilization treatment agent.
本発明に係る処理剤は、アルカリ灰を原料として生成した多硫化物（但し、Sx（ｘ＝６〜１２））を主成分としているために、処理コストを低減することができる。 Since the treatment agent according to the present invention is mainly composed of a polysulfide (where Sx (x = 6 to 12)) produced from alkali ash as a raw material, the treatment cost can be reduced.
また、本発明に係る処理剤の製造方法は、多硫化物（但し、Sx（ｘ＝２〜１２））を主成分とする処理剤を安定して製造することができ、しかも、その生成過程で有毒な硫化水素をはじめとする硫黄の水酸化物を含有する蒸気の発生を抑制することができ、従来必要とされていた蒸気の処理設備や処理工程を省略することができるとともに、処理剤の製造効率を向上させることができる。 In addition, the method for producing a treatment agent according to the present invention can stably produce a treatment agent containing polysulfide (provided that Sx (x = 2 to 12)) as a main component, and its production process. In addition, it is possible to suppress the generation of steam containing sulfur hydroxides including toxic hydrogen sulfide, and it is possible to omit the steam processing equipment and processing steps that have been conventionally required, as well as a processing agent. The production efficiency can be improved.
本発明では、産業廃棄物であり、また、重金属を含有した物質として知られるアルカリ灰を原料とし、それ自体の無害化を図ると同時に、重金属を安定的に固定することができる重金属固定化処理剤や補強剤などとして機能する多硫化物からなる処理剤を生成し、その処理剤を用いて、重金属の固定化や補強などを行うようにしたものである。 In the present invention, it is an industrial waste and is made of alkaline ash known as a substance containing heavy metal, and it is made harmless by itself, and at the same time, heavy metal immobilization treatment that can stably fix heavy metal A treatment agent made of polysulfide that functions as an agent or a reinforcing agent is generated, and the treatment agent is used to fix or reinforce heavy metals.
しかも、生成された処理剤は、生成時に生じた液体状のものに限られず、その沈殿物にも有効成分が含有されており、両方とも有効な処理剤として利用することができるものである。 In addition, the produced treatment agent is not limited to the liquid form produced at the time of production, and the precipitate contains an active ingredient, and both can be used as an effective treatment agent.
また、本発明では、産業廃棄物であるアルカリ灰の一部を原料として用いて重金属固定化処理剤を生成するとともに、その生成された重金属固定化処理剤を用いて残りのアルカリ灰を同時に処理することもできる。これにより、産業廃棄物の処理に要する労力や時間やコストを大幅に低減することができる。 In the present invention, a heavy metal immobilization treatment agent is generated using a part of alkaline ash, which is industrial waste, as a raw material, and the remaining alkali ash is simultaneously treated using the generated heavy metal immobilization treatment agent. You can also Thereby, the labor, time, and cost required for processing industrial waste can be significantly reduced.
具体的には、本発明に係る処理剤は、アルカリ灰を原料として熱水中又は加熱蒸気中で硫黄と反応させることによって生成した多硫化物（但し、Sx（ｘ＝２〜１２））を主成分とする薬剤である。 Specifically, the treating agent according to the present invention is a polysulfide (where Sx (x = 2 to 12)) produced by reacting with sulfur in hot water or steam using alkali ash as a raw material. It is a drug with the main component.
ここで、本発明でいう「アルカリ灰」とは、焼却場、発電所、電気炉、溶解炉、流動床ボイラー等の石炭ボイラー、溶融炉、焼成炉（キルン）などから排出されるｐＨ９以上のアルカリ性の灰及び飛灰の総称であると同時に、これら一種又は二種以上の混合体を含み、また、産業廃棄物で旧来処理の対象物であったもの及びそれとともに生成される水中沈殿物をも含むものを指している。 Here, “alkaline ash” as used in the present invention means a pH of 9 or more discharged from incinerators, power plants, electric furnaces, melting furnaces, coal boilers such as fluidized bed boilers, melting furnaces, kilns, etc. It is a generic name for alkaline ash and fly ash, and at the same time includes one or a mixture of two or more of these, industrial waste that has been the object of traditional treatment, and submerged sediment produced therewith. Also refers to things that include.
また、多硫化物には、反応で生成される液体状のものに限られず、沈殿物も含まれ、この沈殿物には、アルカリ灰と硫黄との熱水反応によって生成される沈殿物に限られず、熱水反応中又は反応後に混入した酸性体や中性体や粘土やシルト等の金属体を含んだ反応材を含んだ沈殿物をも含むものであり、しかも、これらの混合体であってもよく、また濃縮体や乾燥物であってもよい。 Polysulfides are not limited to liquids produced by the reaction, but also include precipitates. These precipitates are limited to precipitates produced by hydrothermal reaction between alkali ash and sulfur. In addition, it also contains precipitates containing reactive materials containing acidic materials, neutral materials, and metal materials such as clay and silt mixed during or after the hydrothermal reaction. It may be a concentrate or a dried product.
かかる処理剤は、汚泥、粉塵、集塵などの主に産業廃棄物に添加混合することによって、鉛・亜鉛・水銀・クロム・マンガン・コバルト・ニッケルなどの重金属と硫黄とが反応し、不溶性硫化物が生成され、重金属を固定化し、これにより、廃棄物（被処理物）から重金属が溶出するのを未然に防止して、無害化する重金属固定化処理剤（廃棄物処理剤）として用いることができる。 Such treatment agents are mainly added to and mixed with industrial waste such as sludge, dust, and dust, so that heavy metals such as lead, zinc, mercury, chromium, manganese, cobalt, and nickel react with sulfur to produce insoluble sulfur. It is used as a heavy metal immobilization treatment agent (waste treatment agent) that prevents the heavy metal from eluting from the waste (object to be treated) and thereby detoxifies it. Can do.
また、自然の岩石、盛土、レンガ、窯業製品などの被処理物に塗布又は含浸させることによって、多硫化物の作用で被処理物の強度を増大させて補強を行うことができる補強処理剤としても用いることができる。 In addition, by applying or impregnating natural rocks, embankments, bricks, ceramic products, etc., as a reinforcing treatment agent that can be reinforced by increasing the strength of the object to be processed by the action of polysulfide Can also be used.
ここで、被処理物としては、自然の岩石、盛土、レンガ、窯業製品に限られず、一般的に用いられる土木用無機質材料や重金属を含む有害物やコンクリート破砕材、有害成分を含む自然石やその微粒体も含まれ、当然に、アルカリ灰やアルカリ灰が生成されるときに発生する水中沈殿物も対象となり、酸性有害物や中性体無機質有害物なども含まれる。 Here, the object to be treated is not limited to natural rocks, embankments, bricks and ceramic products, but is generally used for civil engineering inorganic materials, hazardous materials containing heavy metals, concrete crushing materials, natural stones containing harmful components, The fine particles are also included, and naturally, sediments in water generated when alkali ash or alkali ash is generated are also targeted, and include acidic harmful substances and neutral inorganic harmful substances.
また、木質素材からなる被処理物の表面に塗布又は含浸させることによって、多硫化物の作用で抗菌効果や防虫効果を発揮させることができ、これによって被処理物の保護を行うことができる保護処理剤としても用いることができる。 In addition, by applying or impregnating the surface of an object to be processed made of a wooden material, it is possible to exert an antibacterial effect and an insect-repellent effect by the action of polysulfide, thereby protecting the object to be processed It can also be used as a treating agent.
さらに、金属素材からなる被処理物の表面に塗布又は含浸させることによって、多硫化物の作用で表面に硫化金属膜を形成し、この硫化金属膜によって被処理物の保護を行うことができる保護処理剤としても用いることができる。 Further, by applying or impregnating the surface of the workpiece made of a metal material, a metal sulfide film is formed on the surface by the action of polysulfide, and the workpiece can be protected by this metal sulfide film. It can also be used as a treating agent.
しかも、本発明に係る処理剤は、アルカリ灰を原料として生成した多硫化物（但し、Sx（ｘ＝２〜１２））を主成分としているために、従来の処理剤を使用した場合に問題となる処理剤に含有される有機物の分解による二硫化炭素の発生を防止することができる。 Moreover, since the treatment agent according to the present invention is mainly composed of a polysulfide produced using alkali ash as a raw material (however, Sx (x = 2 to 12)), there is a problem when a conventional treatment agent is used. The generation of carbon disulfide due to the decomposition of the organic matter contained in the treating agent can be prevented.
また、本発明では、反応装置内で原料となるアルカリ灰と硫黄とを混合し、原料となるアルカリ灰中のカルシウム、カリウム、ナトリウム、又はマグネシウムと硫黄を反応させることによって、重金属と反応して固定化する重金属固定化処理剤を製造することができる。硫黄は、固体状のものでも、液体状のものでも、気体状のもの（蒸気化したもの）でもよい。 Further, in the present invention, alkali ash and sulfur as raw materials are mixed in a reactor, and reacted with heavy metals by reacting calcium, potassium, sodium, or magnesium and sulfur in the raw alkali ash. A heavy metal immobilization treatment agent to be immobilized can be produced. Sulfur may be solid, liquid, or gaseous (vaporized).
この重金属固定化処理剤は、原料とは異なるアルカリ灰と反応させることによってアルカリ灰中に含有される重金属を固定化することができる。 This heavy metal immobilization treatment agent can immobilize heavy metals contained in alkali ash by reacting with alkali ash different from the raw material.
この原料となるアルカリ灰に、石、粘土、真砂、又は灰を混入させてもよい。たとえば、石炭フライアッシュと硫黄とを熱水反応させ、一定時間経過後に酸性スラッジを混合させたところ、石炭フライアッシュと酸性スラッジの両方を無害化させることができた。 Stone, clay, pure sand, or ash may be mixed into the alkali ash that is the raw material. For example, when coal fly ash and sulfur were reacted with hot water and acidic sludge was mixed after a certain period of time, both coal fly ash and acidic sludge could be rendered harmless.
また、反応装置内で原料となるアルカリ灰と硫黄とを混合し、原料となるアルカリ灰中のカルシウム、カリウム、ナトリウム、又はマグネシウムと硫黄を反応させて重金属固定化処理剤を生成し、この重金属固定化処理剤を用いて酸性体中の重金属を固定化させることによって、アルカリ性を示す重金属固定化処理剤を中和処理する必要がなくなり、中和処理のための作業やコストを削減することができる。 In addition, alkaline ash and sulfur as raw materials are mixed in the reactor, and calcium, potassium, sodium, or magnesium and sulfur in the raw alkaline ash are reacted to produce a heavy metal immobilizing treatment agent. By immobilizing heavy metals in acidic bodies using an immobilizing agent, there is no need to neutralize the heavy metal immobilizing agent exhibiting alkalinity, and the work and costs for the neutralizing treatment can be reduced. it can.
また、反応装置内で廃棄物としてのアルカリ灰の一部と硫黄とを混合し、このアルカリ灰中のカルシウム、カリウム、ナトリウム、又はマグネシウムと硫黄を反応させて重金属固定化処理剤を生成し、この重金属固定化処理剤を用いて残りのアルカリ灰中の重金属を固定化することによって、廃棄物全体を処理することができ、経済性を向上させることができる。 Moreover, a part of alkaline ash as waste and sulfur are mixed in the reactor, and calcium, potassium, sodium, or magnesium and sulfur in this alkaline ash are reacted to produce a heavy metal fixing treatment agent, By immobilizing the heavy metal in the remaining alkali ash using this heavy metal immobilizing agent, the entire waste can be treated and the economy can be improved.
また、反応装置内で原料となるアルカリ灰と硫黄とを混合し、原料となるアルカリ灰中のカルシウム、カリウム、ナトリウム、又はマグネシウムと硫黄を反応させて補強処理剤を生成し、この補強処理剤を用いて被処理物の補強を行うことができる。 Also, the alkaline ash and sulfur as raw materials are mixed in the reactor, and calcium, potassium, sodium, or magnesium and sulfur in the raw alkaline ash are reacted to produce a reinforcing agent, and this reinforcing agent The object to be processed can be reinforced using the.
たとえば、地盤や路床の強度改良を目的として、飛灰と、硫黄、真砂、粘土とを混合反応させた場合には、重金属安定剤としての性能以外に金属との結合や、灰中成分（カルシウム、マグネシウム、カリウム、ナトリウム、シリカ）と反応させ、これをローラ等で転圧することで地耐力の強化を図ることができる。 For example, when fly ash is mixed and reacted with sulfur, masago, or clay for the purpose of improving the strength of the ground or roadbed, in addition to its performance as a heavy metal stabilizer, By reacting with calcium, magnesium, potassium, sodium, silica) and rolling this with a roller or the like, the earth strength can be enhanced.
また、反応装置内で原料となるアルカリ灰と硫黄とを混合し、原料となるアルカリ灰中のカルシウム、カリウム、ナトリウム、又はマグネシウムと硫黄を反応させて処理剤を生成し、この処理剤の生成と同時に原料となるアルカリ灰の沈殿生成物を生成することができる。 In addition, alkaline ash and sulfur as raw materials are mixed in the reactor, and a treatment agent is produced by reacting calcium, potassium, sodium, or magnesium and sulfur in the alkaline ash as raw material. At the same time, a precipitation product of alkaline ash as a raw material can be generated.
また、反応装置内で原料となるアルカリ灰と硫黄とを混合し、原料となるアルカリ灰中のカルシウム、カリウム、ナトリウム、又はマグネシウムと硫黄を反応させて処理剤を生成し、この処理剤の生成と同時に原料となるアルカリ灰の沈殿生成物からなる重金属安定剤を生成することができる。 In addition, alkaline ash and sulfur as raw materials are mixed in the reactor, and a treatment agent is produced by reacting calcium, potassium, sodium, or magnesium and sulfur in the alkaline ash as raw material. At the same time, it is possible to produce a heavy metal stabilizer comprising a precipitation product of alkaline ash as a raw material.
提供するものである。 It is to provide.
また、反応装置内で原料となるアルカリ灰と硫黄とを混合し、原料となるアルカリ灰中のカルシウム、カリウム、ナトリウム、又はマグネシウムと硫黄を反応させ、蒸発減水させることによって金属反応剤を生成することができる。 Moreover, the alkali ash and sulfur used as raw materials are mixed in the reaction apparatus, and calcium, potassium, sodium, or magnesium in the raw alkali ash is reacted with sulfur to reduce the evaporation, thereby generating a metal reactant. be able to.
また、反応装置内で原料となるアルカリ灰と硫黄とを混合し、原料となるアルカリ灰中のカルシウム、カリウム、ナトリウム、又はマグネシウムと硫黄を反応させ、蒸発減水させ、さらに乾燥させることによって金属反応剤を生成することができる。 In addition, alkali ash and sulfur as raw materials are mixed in the reactor, and calcium, potassium, sodium, or magnesium in the raw alkaline ash is reacted with sulfur, evaporated to reduce water, and further dried to react with metal. An agent can be produced.
また、反応装置内で原料となるアルカリ灰と硫黄とを混合し、原料となるアルカリ灰中のカルシウム、カリウム、ナトリウム、又はマグネシウムと硫黄を反応させ、液状の処理剤と沈殿生成物からなる固体状の処理剤とを生成し、液体状の処理剤から濃縮液を生成したり、液体状の処理剤を乾燥させて水溶性の粉状又は粒状の処理剤を生成したり、さらには、沈殿生成物を加熱濃縮してウエット状又は乾燥状の処理剤を生成することができる。 In addition, the alkali ash and sulfur as raw materials are mixed in the reactor, and calcium, potassium, sodium, or magnesium and sulfur in the raw alkaline ash are reacted to form a solid consisting of a liquid processing agent and a precipitation product. A liquid treatment agent to produce a concentrated liquid, or to dry a liquid treatment agent to produce a water-soluble powdery or granular treatment agent. The product can be heated and concentrated to produce a wet or dry treatment agent.
上記した処理剤は、アルカリ灰を原料として多硫化物（但し、Sx（ｘ＝２〜１２））を安定かつ安全に生成する必要があり、そのための方法としては、アルカリ灰に含有される水酸化カリウム、水酸化マグネシウム、水酸化カルシウム、水酸化ナトリウムのいずれか又はこれらの混合物と硫黄とを密閉容器内で蒸気の排出をすることなく98℃〜345℃の高圧下で撹拌混合しながら反応させることによって生成する方法がある。 The above-mentioned treatment agent needs to generate polysulfide (however, Sx (x = 2 to 12)) using alkali ash as a raw material in a stable and safe manner, and as a method therefor, water contained in alkali ash is used. Reaction while stirring and mixing any one of potassium oxide, magnesium hydroxide, calcium hydroxide, sodium hydroxide, or a mixture thereof and sulfur in a sealed container at a high pressure of 98 ° C to 345 ° C without discharging steam. There is a method to generate by.
たとえば、水酸化カルシウムと硫黄とを用いた場合には、消石灰と硫黄と水とを混合することによって生成でき、このとき、
Ca(OH)2→Ca++＋２OH--
Ca++＋S→CaS
の反応が起こる。
For example, when calcium hydroxide and sulfur are used, they can be produced by mixing slaked lime, sulfur and water,
Ca (OH) 2 → Ca ++ + 2OH -
Ca ++ + S → CaS
Reaction occurs.
このCaSは、
２CaS＋４OH--→H2S＋Ca(OH)2＋S＋Ca＋O2
となる。
This CaS is
2CaS + 4OH - → H 2 S + Ca (OH) 2 + S + Ca + O 2
It becomes.
ここで、従来の製法では、一部の硫化水素及び酸素が蒸気として大気に開放されていたが、本発明では、この反応を密閉容器内で行わせることで蒸気の排出をしないようにしている。 Here, in the conventional manufacturing method, a part of hydrogen sulfide and oxygen was released to the atmosphere as steam, but in the present invention, this reaction is performed in a sealed container so that the steam is not discharged. .
そのため、上記反応が正確に進んで、
H2S＋Ca(OH)2＋S＋Ca→Ca(HS)2＋Ca(OH)2
となる。
Therefore, the above reaction proceeds accurately,
H 2 S + Ca (OH) 2 + S + Ca → Ca (HS) 2 + Ca (OH) 2
It becomes.
また、CaSは、
２CaS＋２H2O→Ca(HS)2＋Ca(OH)2
となる。
CaS is
2CaS + 2H 2 O → Ca (HS) 2 + Ca (OH) 2
It becomes.
さらに、CaSは、
CaS＋（ｘ−１）S→CaSx
となって、CaSxが安定して生成される。
In addition, CaS
CaS + (x-1) S → CaSx
Thus, CaSx is stably generated.
これは、水酸化カルシウムを用いた場合に限られず、水酸化カリウム、水酸化マグネシウム、水酸化カルシウム、水酸化ナトリウムのいずれか又はこれらの混合物を用いた場合でも、Sxを含有する処理剤を安定して生成できる。 This is not limited to when calcium hydroxide is used, and even when potassium hydroxide, magnesium hydroxide, calcium hydroxide, sodium hydroxide, or a mixture thereof is used, the treatment agent containing Sx is stabilized. Can be generated.
特に、水酸化カリウム、水酸化マグネシウム、水酸化カルシウム、水酸化ナトリウムのいずれか又はこれらの混合物と硫黄とを硫黄の粒子表面に付着したカリウム、マグネシウム、カルシウム、又はナトリウムを破砕し剥離させるように撹拌混合しながら反応させることによって多硫化物を主成分とする処理剤をより安定して生成することができる。 In particular, potassium hydroxide, magnesium hydroxide, calcium hydroxide, sodium hydroxide, or a mixture thereof and sulfur and potassium, magnesium, calcium, or sodium adhering to the surface of the sulfur particles are crushed and peeled off. By reacting while stirring and mixing, a treatment agent mainly composed of polysulfide can be generated more stably.
また、硫黄の溶解温度以上の温度で反応を行わせた場合には、多硫化物（但し、Sx（ｘ＝８））を主成分とする処理剤を安定して生成することができる。 In addition, when the reaction is performed at a temperature equal to or higher than the melting temperature of sulfur, a treatment agent containing polysulfide (however, Sx (x = 8)) as a main component can be stably generated.
また、硫黄と熱水との混合液に、水酸化カリウム、水酸化マグネシウム、水酸化カルシウム、水酸化ナトリウムのいずれか又はこれらの混合物を所定量連続的に混入させた場合には、多硫化物（但し、Sx（ｘ＝８〜１０））を主成分とする処理剤を安定して生成することができる。 In addition, when a predetermined amount of potassium hydroxide, magnesium hydroxide, calcium hydroxide, sodium hydroxide or a mixture thereof is continuously mixed in a mixed solution of sulfur and hot water, polysulfide However, it is possible to stably produce a treatment agent mainly composed of Sx (x = 8 to 10).
また、水酸化カリウム、水酸化マグネシウム、水酸化カルシウム、水酸化ナトリウムのいずれか又はこれらの混合物と硫黄と熱水との混合液に低温環境下（−２０℃〜０℃）で消石灰を混入させた場合には、多硫化物（但し、Sx（ｘ＝６〜１２））を主成分とし、被処理剤を固化することができるミルク状の固化剤を含んだ処理剤を安定して生成することができる。 Moreover, slaked lime is mixed in a mixed solution of potassium hydroxide, magnesium hydroxide, calcium hydroxide, sodium hydroxide or a mixture thereof and sulfur and hot water in a low temperature environment (−20 ° C. to 0 ° C.). In this case, a treatment agent containing a milk-like solidifying agent, which is mainly composed of polysulfide (however, Sx (x = 6 to 12)) and can solidify the treatment agent, is stably generated. be able to.
また、水酸化カリウム、水酸化マグネシウム、水酸化カルシウム、水酸化ナトリウムのいずれか又はこれらの混合物と硫黄と熱水との混合液に低温環境下（−３０℃〜−２５℃）でカルシウムを混入させた場合には、多硫化物（但し、Sx（ｘ＝８））を主成分とする処理剤を安定して生成することができる。 In addition, calcium is mixed in a mixed solution of potassium hydroxide, magnesium hydroxide, calcium hydroxide, sodium hydroxide or a mixture thereof and sulfur and hot water in a low temperature environment (-30 ° C to -25 ° C). In this case, it is possible to stably produce a treatment agent containing polysulfide (however, Sx (x = 8)) as a main component.
また、予め１００μ以下（好ましくは、５０μ以下）に粉砕した硫黄と、水酸化カリウム、水酸化マグネシウム、水酸化カルシウム、水酸化ナトリウムのいずれか又はこれらの混合物を粉体又はシルト状態で用いた場合には、多硫化物（但し、Sx（ｘ＝１０〜１２））を主成分とする処理剤を安定して生成することができる。 In addition, when sulfur pulverized to 100 μm or less (preferably 50 μm or less), potassium hydroxide, magnesium hydroxide, calcium hydroxide, sodium hydroxide or a mixture thereof is used in a powder or silt state Can stably produce a treating agent mainly composed of polysulfide (however, Sx (x = 10 to 12)).
また、原料となるアルカリ灰として松浦石灰火力発電所産フライアッシュ（炭種;マッセルブルグ50％、ドレイトン50％の混焼により発生したもので、アルカリ度ＰＨ13.5）を用い、フライアッシュ20重量部、硫黄20重量部、水100重量部の配合比とした。 In addition, fly ash from Matsuura Lime Thermal Power Plant (coal species; generated by co-firing 50% Musselburg and 50% Drayton, alkalinity PH13.5) as alkali ash as raw material, 20 parts by weight fly ash, The mixing ratio was 20 parts by weight of sulfur and 100 parts by weight of water.
そして、まず、フライアッシュ20重量部と水100重量部を反応缶に入れ、上蓋を閉じ、混合機を作動させて10分程度混合する。 First, 20 parts by weight of fly ash and 100 parts by weight of water are placed in a reaction can, the upper lid is closed, and the mixer is operated to mix for about 10 minutes.
次に、混合機を停止後、上蓋を開放し、硫黄20重部を投入する。 Next, after stopping the mixer, the top lid is opened and 20 parts by weight of sulfur are introduced.
次に、安全弁を設定し目的とする排気圧・約2.5kg/cm2にセットし排水バルブ及冷却バルブを開放するとともに冷却水入口バルブを開放して通水する。 Then, passing water by opening the cooling water inlet valve with set to a discharge pressure, about 2.5 kg / cm 2 for the purpose to set the safety valve to open the drain valve及cooling valve.
次に、上蓋を閉じ、混合機を作動させて混合する。 Next, the upper lid is closed and the mixer is operated to mix.
次に、バーナに点火して、圧力計と温度計とを確認し、混合しながら昇温する。この時に、圧力は2.5kg/cm2以下とし温度は90℃以上とする必要がある。 Next, the burner is ignited, the pressure gauge and the thermometer are confirmed, and the temperature is raised while mixing. At this time, the pressure must be 2.5 kg / cm 2 or less and the temperature must be 90 ° C. or more.
次に、温度計の表示が110℃に達してから、約30分間混合反応させる。 Next, after the thermometer display reaches 110 ° C., the mixture is reacted for about 30 minutes.
次に、バーナを停止し、圧力計が下降するまで放置し、安定したら安全弁により最終残圧を完全に排出し、大気圧と同化させる。 Next, the burner is stopped and left until the pressure gauge descends. When the pressure gauge is stabilized, the final residual pressure is completely discharged by the safety valve and assimilated with atmospheric pressure.
次に、混合機を停止させ、上蓋を開放し、排出バルブを開放して、沈澱物及び液体を排出して、これらを回収する。 Next, the mixer is stopped, the upper lid is opened, the discharge valve is opened, the precipitate and liquid are discharged, and these are collected.
次に、回収物を冷却し、沈澱分離し薬液と沈澱物を得る。 Next, the recovered product is cooled and separated by precipitation to obtain a chemical solution and a precipitate.
このようにして、薬液98重量部と沈澱物102重量部を得ることができる。 In this way, 98 parts by weight of the chemical solution and 102 parts by weight of the precipitate can be obtained.
この薬液は、多硫化カルシウム、多硫化カリウムを含有しており、液比重が1.02g/ccで黄緑色のpH10の液体であった。 This chemical solution contained calcium polysulfide and potassium polysulfide, and had a liquid specific gravity of 1.02 g / cc and a yellow-green pH 10 liquid.
また、原料とし焼却場飛灰ＰＨ13.5を用いたところ、多硫化カルシウムを含有した液比重が1.15g/ccの茶色のpH19の液体を得た。 Further, when incineration fly ash PH13.5 was used as a raw material, a brown pH19 liquid containing calcium polysulfide and having a liquid specific gravity of 1.15 g / cc was obtained.
そして、上記pH10の薬液30重量部とpH19の薬液5重量部とをそれぞれ用いて、pH13.5のアルカリ灰（鉛含有量1300mg/kg/dry、溶出値12mg/L）100重量部及び調整水40重量部を混合したところ、環告46号（溶出試験）に従って分析すると、上記pH10の薬液を用いた場合には、鉛溶出12mg/Lから0.005mg/Lに低減され、また、上記pH13.5の薬液を用いた場合には、鉛溶出12mg/Lから0.001/mg/L以下に低減され、最も固定化が困難な鉛を固定化することができ、重金属安定剤としての十分な効果を発揮することが確認された。 Then, using 30 parts by weight of the above-mentioned chemical solution at pH 10 and 5 parts by weight of the chemical solution at pH 19, 100 parts by weight of alkaline ash at pH 13.5 (lead content 1300 mg / kg / dry, elution value 12 mg / L) and adjustment water When 40 parts by weight were mixed and analyzed according to Circular 46 (dissolution test), the lead elution was reduced from 12 mg / L to 0.005 mg / L when the pH 10 chemical solution was used, and the pH 13. When 5 chemicals are used, lead elution is reduced from 12 mg / L to 0.001 / mg / L or less, and the most difficult to immobilize lead can be immobilized. It has been confirmed that it works.
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| CN107384408A (en) * | 2017-09-20 | 2017-11-24 | 湖南景翌湘台环保高新技术开发有限公司 | A kind of farmland pollution soil heavy metal passivant and its preparation and application |
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| JP4850141B2 (en) * | 2007-07-31 | 2012-01-11 | 株式会社環境アネトス | Decomposition method for waste materials containing asbestos |
| CN108785951A (en) * | 2017-05-02 | 2018-11-13 | 广州市川清环保科技有限公司 | The insoluble inorganic agent of heavy metal and the insoluble processing method of heavy metal |
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| JP4598743B2 (en) * | 2006-10-16 | 2010-12-15 | 株式会社環境アネトス | Method for producing a drug mainly composed of polysulfide (however, Sx (x = 2 to 12)) |
| CN107384408A (en) * | 2017-09-20 | 2017-11-24 | 湖南景翌湘台环保高新技术开发有限公司 | A kind of farmland pollution soil heavy metal passivant and its preparation and application |
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